Supporting Information...Supporting Information Bajaj et al. 10.1073/pnas.0900975106 SI Text General Procedure. Compound II (Scheme S1) bearing ammo- nium end groups were synthesized

Supporting InformationBajaj et al. 10.1073/pnas.0900975106SI TextGeneral Procedure. Compound II (Scheme S1) bearing ammo-nium end groups were synthesized through the reaction of1,1,1-triphenyl-14,17,20,23-tetraoxa-2- thiapentacosan-25-ylmethanesulphonate (I) with corresponding substituted N,N-dimethylamines during 48 h at �35 °C. The trityl protected thiolligand (II) was dissolved in dry DiChloroMethane (MethyleneChloride, DCM) and an excess of trif luoroacetic acid (TFA, �20eq) was added. The color of the solution was turned to yellowimmediately. Subsequently, triisopropylsilane (TIPS, �1.2 eq)was added to the reaction mixture. The reaction mixture wasstirred for �5 h under Ar condition at room temperature. Thesolvent and most TFA and TIPS were distilled off under reducedpressure. The pale yellow residue was further dried in highvacuum. The product (L) formation was quantitative and theirstructure was confirmed by NMR. The yields were �95%.

Compound L1. 1H NMR (400MHz, CDCl3, TMS): � 3.95 (br, 2H,-OCH2-(CH2N)-), 3.81–3.72 (m, 1H, HCyclo), 3.69–3.53 (m, 14H,

-CH2O- � -CH2N-), 3.49 (t, 2H, -CH2O-), 3.11 (s, 6H,-(CH3)2N-), 2.91 (s, 3H, CH3SO-

3-), 2.52 (q, 2H, -CH2S-), 2.23 (d,2H, HCyclo), 1.99 (d, 2H, HCyclo), 1.78–1.52 (m, 4H, -(SCH2)CH2� -CH2(CH2O)-), 1.51–1.12 (m, 21H, SH � -CH2- � HCyclo).

Compound L2. 1H NMR (400MHz, CDCl3, TMS): � 8.37 (d, 1H,HAr), 7.98 (d, 1H, Ar-), 7.69–7.61 (m, 3H, HAr), 7.59–7.48 (m,1H, HAr), 4.38 (br, 2H,-NCH2-Ar), 3.76 (br, 2H, -OCH2-(CH2N)-), 3.72–3.62 (m, 14H, -CH2O- � -CH2N-), 3.61–3.55 (m,2H, -CH2O-), 3.23 (s, 6H, -(CH3)2N-), 3.07 (s, 3H, CH3SO-

3-),2.52 (q, 2H, -CH2S-), 1.67–1.51 (m, 4H, -(SCH2)CH2 �-CH2(CH2O)-), 1.35–1.21 (m, 15H, -SH � -CH2-).

Compound L3. 1H NMR (400MHz, CDCl3, TMS): � 3.94 (br, 2H,-OCH2-(CH2N)-), 3.78 (br, 1H, -OH), 3.75–3.52 (m, 16H,-CH2O- � -CH2N- � -CH2-OH), 3.48 (t, 2H, -CH2O-), 3.39–3.31(m, 2H,-NCH2-), 3.25 (s, 6H, -(CH3)2N-), 2.89 (s, 3H, CH3SO-

3-),2.52 (q, 2H, -CH2S-), 2.35–2.26 (m, 2H, -(NCH2)CH2-), 1.70–1.52 (m, 4H, � (SCH2)CH2 � -CH2(CH2O)-), 1.36–1.21 (m,15H, -SH � -CH2-).

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Fig. S1. Dynamic light scattering (DLS) and zeta potential (ZP) of NP1-NP3 were measured in 5 mM phosphate buffer at pH 7.4. The overall size and chargeof these cationic NPs were on the range of 10–12 nm and �21 mV respectively.



Fig. S2. Binding constants (logKS), binding stoichiometries (n) between polymer PPE-CO2 and fluorescence titration curves for the complexation of PPE-CO2

(100 nM) with various cationic gold nanoparticles as showed. The intensity changes at 465 nm were followed by adding several concentrations of NPs with anexcitation wavelength of 430 nm. The red solid lines represent the best curve-fitting.



Fig. S3. (a) Chemical structures of the nine nanoparticles screened for cell sensing studies. (b) Jackknifed classification matrix obtained through LDA analysisfor nine nanoparticles for all cell sensing studies.



Scheme S1. Synthesis of ligands for nanoparticles NP1, NP2, NP3 (1–3).

1. Brust M, Walker M, Bethell D, Schiffrin DJ, Whyman R (1994) Synthesis of thiol-derivatised gold nanoparticles in a two-phase liquid–liquid system. J Chem Soc Chem Commun 801–802.2. Hostetler MJ, Templeton AC, Murray RW (1999) Dynamics of place-exchange reactions on monolayer-protected gold cluster molecules. Langmuir 15:3782–3789.3. You CC, et al. (2007) Detection and identification of proteins using nanoparticle-fluorescent polymer ‘‘chemical nose’’ sensors. Nat Nanotechnol 2:318–323.



Table S1. Training matrix of fluorescence response patterns (F0 � F) of NP-PPE sensor array (NP1–NP3) against several normal andcancerous cell lines with identical cell numbers

Cell lines NP1 NP2 NP3

HeLa 108.437 �22.619 131.272HeLa 96.849 �32.549 135.131HeLa 89.927 33.928 141.366HeLa 101.968 36.883 138.971HeLa 102.661 105.368 136.431HeLa 91.654 �38.012 134.211MCF7 88.523 �65.715 156.947MCF7 114.97 26.743 137.731MCF7 105.638 27.744 153.065MCF7 105.96 �26.903 142.949MCF7 117.061 17.557 155.298MCF7 114.596 6.609 150.304HepG2 47.544 �64.227 18.799HepG2 66.327 �21.701 23.522HepG2 80.899 26.59 23.866HepG2 64.620 7.153 17.854HepG2 62.46 26.967 19.176HepG2 56.912 �136.285 19.934NT2 19.087 �109.73 74.753NT2 8.361 �123.024 74.926NT2 73.837 �32.683 85.101NT2 58.277 �34.835 77.39NT2 22.529 �48.185 90.413NT2 �5.155 �77.017 56.566





MCF7 88.523 �65.715 156.947MCF7 114.97 26.743 137.731MCF7 105.638 27.744 153.065MCF7 105.96 �26.903 142.949MCF7 117.061 17.557 155.298MCF7 114.596 6.609 150.304MCF10A 36.403 �133.662 52.088MCF10A 38.125 42.26 50.506MCF10A 27.901 �41.355 60.088MCF10A 37.498 8.538 56.473MCF10A 25.869 �73.426 41.947MCF10A 30.117 �144.145 52.737MDMB231 49.212 �3.683 101.597MDMB231 78.188 0.156 111.938MDMB231 52.489 �40.314 100.431MDMB231 49.228 �5.52 105.549MDMB231 64.227 �23.985 102.052





CDBgeo 13.861 �24.620 51.592CDBgeo 37.105 �21.639 59.431CDBgeo 36.536 �36.333 68.922CDBgeo 44.061 �26.607 55.739CDBgeo 30.166 �17.268 56.664CDBgeo 20.477 �29.478 48.557V14 35.127 �15.553 96.790V14 74.667 �26.552 90.021V14 77.513 �7.651 75.153V14 69.386 �23.164 69.885V14 73.883 �1.544 77.78V14 50.385 �19.679 82.247TD 39.278 �86.639 85.797TD 39.432 �90.846 71.702TD 36.815 �82.081 75.508TD 56.404 �74.041 75.384TD 32.872 �62.026 74.187TD 23.431 �64.688 58.341



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Supporting Information...Supporting Information Bajaj et al. 10.1073/pnas.0900975106 SI Text General Procedure. Compound II (Scheme S1) bearing ammo- nium end groups were synthesized